Dehydrogenation catalyst and process



United States Patent DEHYDROGENATION CATALYST AND PROCESS Emory W. litzer and Lucien Bag'netto, In, Bartlesville,

Okla. assignors to Phillips Petroleum Company, a corporatron of Delaware No Drawing. Application August 29, 1956 Serial No. 606,794

6 Claims. (Cl. 260-680) Patented May 26, 1959 chromium oxideand/or cupric oxide. In the catalyst mixture, it is preferred that the potassium appear in the final form as the carbonate. Equivalent amounts of other potassium compounds can also be usedin making the catalyst. These other compounds can be converted to the carbonate during the preparation of the catalyst or may convert to the carbonate during the use of the catalyst. Suitable compounds include potassium hydroxide, potassium carbonate, potassium nitrate, potassium acetate and similar materials; I

In-preparing the catalysts the Mg, Fe, Cr, and/or Co are present in the following proportions calculated on the basis of their oxides.

The potassium carbonate is present in a weight percent of at least about or more, preferably in a weight percent of between about 30 and about 40 percent.

or mixtures thereof at elevated temperatures to remove carbonaceous materials. Regenerative treatment decreases the time during which the dehydrogenation reaction can be carried out, since the flow of hydrocarbon must be shut off during regeneration.

With some types of dehydrogenation catalysts it has been the practice to use small amounts of alkali oxides and alkaline earth oxides as promoters. Generally, these materials are used in amounts up to about 10.0 percent by weight. They tend to promote the dehydrogenation reaction and also aid in reducing the necessity for frequent regeneration. However, even with the use of promoting compounds, it has been necessary to periodically regenerate the catalysts, usually after only a few hours of operation. It is desirable, therefore, to provide Although the catalysts of this invention can contain either oxides of chromium or copper, it has been found that the preferred catalysts are those which contain chromium. As will be hereinafter shown, the chromium containing catalyst is much more active than the copper catalyst, having otherwise the same composition.

Thev catalysts are. prepared by a number of methods which include mixing or co-grinding of the metal oxides, by thermally decomposing salts of the metals, by coprecipitating hydrous oxides, etc. In one preferred metha catalyst suitable for use in dehydrogenation which can be used for extended periods with little or no loss in catalytic properties.

It is an object of this invention to provide such a catalyst.

It is another object of this invention to provide an im- .ing mono-olefins, alkylpyridines and alkylaromatics under suitable conversion conditions with a catalyst comprising oxides of iron, magnesium and chromium and/or copper and potassium carbonate, the potassium carbonate being present in a weight percent of at least about 30 percent based on the total catalyst. In a more specific aspect, the dehydrogenation process is carried out at a temperature of between about 1050 F. and about 1300 F. and with a steam to hydrocarbon ratio of between about 5 to 1 and about 30 to 1.

The catalysts of this invention comprise mixtures of the oxides of magnesium, iron and chromium and potassium i More usually, the metals other than potascarbonate. sium are present as magnesium oxide, ferric oxide and 0d, the proper amounts of the oxide are milled together, for example in a hammer mill, following which a pelleting aid such as tannic acid is added to the mixture and subsequently the catalyst is pelleted in a suitable machine, such as a Stokes tablet machine. The catalyst pellets can also be formed by extrusion with satisfactory results. The final pellets are dried at temperatures of between about 200 F. and about 350 F. for a period of 1 to 24 hours, followed by a final heating at increasing temperatures to as high as 1050 F. to 1300 F., for an additional 1 to 24 hours. The catalyst can be prepared in any suitable form depending on the type of reaction system in which they are to be used, for example they can be prepared in the form of pellets, Berl saddles, etc., or they can be finely divided to provide catalysts suitable for fluidization.

The organic compounds treated in this process are mono-olefins, alkyl pyridines and alkyl aromatics containing at least 2 carbon atoms in the alkyl group. Suitable mono-olefins are those having 4 to 10 carbon atoms such as, for example, butene-l, butene-Z, methylethyl ethylene, trimethylethylene, isopropyl ethylene, pentene-l, hexene-l, etc. Specific dehydrogenation reactions include the dehydrogenation of 2-butene to butadiene and 2-methyl-'2- butene to isoprene.

The dehydrogenation of ethyl benzene to styrene and the dehydrogenation of 2-methyl-5-ethylpyridine to 2- methyl-S-vinylpyridine are also important applications of the invention. The process is applicable generally to the feed materials stated although'mono-olefins of 8 or less carbon atoms and alkylbenzenes' or alkylpyridines with 1 to 4 alkyl groups each having '6 or less carbon atoms with at least one alkyl group of two or more carbon atoms are most applicable from the standpoint of yield, selectivity and economics.

The dehydrogenative reaction is carried out at an elevated temperature between about 1050" F. and about v1300 F. and with a steam to olefin ratio of between about 5 to 1 and about 30 to 1 by volume. The pressure preferably is maintained at a low level, usually at atmospheric or slightly above-atmospheric. The process is eration of catalyst.

.. aaaaaee suspended catalyst techniques can be used. of operation it is usually preferred to maintain a gas space velocity of between about 50 and about 2500 volumes per hour of olefin per volume of catalyst. Advantageously, 0.5 to 2 mol percent of carbon dioxide, based on the total feed, can be introduced to the reaction zone to minimize migration of the potassium compound through the catalyst bed and possible loss thereof from the reaction zone. In some cases, the catalyst can be improved by calcining the iron oxide before making the catalyst. '..'The.catalyst of the present invention is particularly advantageous in that it allows substantially continuous operation without the necessity of frequent periodic regen- The operation under substantially auto-regenerative conditions is facilitated by the high percentage of potassium carbonate in the catalyst. The potassium carbonate promotes the water-gas reaction so that the carbon, as it forms, reacts with steam present in the gases to produce oxides of carbon which are carried out with the reaction mixture. Thus, only a small equilibrium amount of carbon is present on the catalyst and this is insufficient to interfere substantially with the dehydrogenation reaction.

f The following specific catalysts and tests are presente in illustration of the catalyst and process of this invention: CATALYST PREPARATION Catalyst I This catalyst was prepared by mixing proper amounts of magnesium oxide, ferric oxide, chromium sesquioxide and potassium carbonate and grinding the mixture in a Raymond hammer mill to pass a 50 mesh screen. Following this, 2.4 precent tannic acid (in an amount equivalent to' 5 percent of the catalyst by weight) was mixed with the catalyst, the mixture was sieved through a 28 mesh sieve, after which graphite was added in an amount equal to /2 of 1 percent of the catalyst by weight. This mixture was then formed to A inch tablets, ground to 12 mesh and finally formed to /8 inch tablets. The final treatment comprised heating the tablets at 350 F. for 16 hoursand then at increasing temperatures to 1100 F. for an additional 18 hours. The catalyst composition was magnesium oxide 42.2 weight percent, potassium car- .bonate 35.2 weight percent, ferric oxide 18.4 weight percent and chromium sesquioxide 4.2 percent.

Catalyst II This catalyst was prepared in the same manner as Catalyst I and had a final composition of magnesium oxide 422, potassium carbonate 35.2 percent, ferric oxide 18.4 and cupric oxide 4.2 percent.

Catalyst III This catalyst was prepared in the same manner as Catalyst l and had a final composition of magnesium oxide 57.4 percent, potassium carbonate 20.0 percent, ferric oxide-18.4 and cupric oxide 4.2 percent.

Catalyst IV This catalyst was prepared in the same manner as Catalyst I and had a final composition of magnesium oxide 70.7 percent; potassium carbonate 7.1 percent; ferric oxide 18.1 percent and cupric oxide 4.1 percent.

EXAMPLES In this type.

Temperature Temperature 1130 to 1190 F. 7 Pressure Atmospheric.

Butylene SV 400 cubic feet per hour/ cubic foot.

The tests were carried out over time periods of 24, 48 and 96 hours with steaming between periods as follows:

1 For example, operation on a 24 hour cycle would include: Dehydrogenation oi butene-2 for 23 hours, followed by steaming in the absence or butane-2 for 1 hour, followed by dehydrogenation of butene-Z for 23 hours, followed by steaming in the absence of hutene2 for 1 hour, etc. In each case, the steaming was carried out at the same temperature as the dehydrogenation reaction and the quantity of steam was the same as that used during dehydrogenation.

In Table 1 there is presented a series of consecutive cycles with Catalyst 1:

TABLE I Average Hours M01 Percent Temper- Since ature, 8team- F. ing a Conver- Yield e Selecslon b tlvity 4 B Number of hours of dehydrogenation since the catalyst was last steamed in the absence oi butane-2 feed.

b Mols butene-Z destroyed/100 mols charged.

. e Mols butadiene produced/100 mols butane-2 charged.

4 (Yield/Conversion) X 100.

Itis to be noted that the runs of Table I cover a catalyst life of approximately 100 days or 2400 hours. During this time the catalyst was operating during a number of operating cycles of various time durations, namely from 22 hours to as high as 96 hours. Referring to the data in the table, it is apparent that this catalyst retained a high degree of activity and selectivity over extended periods of time. For example, at a catalyst age of 31.75 days, it is to be noted that after 94 hours of operation the percent conversion, yield and selectivity were 22.2, 19.5 and 87.8 respectively. This compares very favorably with the catalyst aging 32.88 days, where after only four hours of operation on the current cycle the conversion, yield, and selectivity were 23.0, 20.1 and 87.4, respectively. Additional tests throughout the series of cycles indicate the same small degree of change in these properties.

If the over-all life of the catalyst is considered, it is to be noted that 32.88 days after 4 hours of operation, the conversion, yield, and selectivity were 23.0, 20.1 and 87.4, as compared to the catalyst of 100.38 days which 7 after four hours of operation showed a conversion, yield and selectivity of 22.3, 19.3 and 86.5. During this period of operation of over 1,600 hours, there was practically no change in the conversion, yield, and selectivity of the catalyst.

In Table II are presented average figures for the conversion,'-yield and selectivityrof thecycles ofi'lable I from 31.75 daysto 100.38 days.

, TABLE V arreo'r OFDEHYDBOGENATION .raaron LENGTH TABLE II Catalyst IV Catalyst II CatalystI Catalyst III Hours after stearn- Average Average Mol Percent ing 4 44 4 44 4 44 4 44 Average Temperature, HoursSinc'e F. Steaming 1 I Conversion Yield Selectivity M01 Percent 21.9 21.5 28.2 29.7 15.1 12.3 Yield 01 25.3 9.7 21.9 19.8 29.8 29.5 18.6 17.8 Butadiene. 22.1 9.0 18.2 18.3 20.1 19.5 18.8. 17.8 1,150 42; 20.9 18.1 86.6 10 1,150 I 4 22.4' 19.3 85.9 Average 23.7 4 20.7 19.9 26.0 26.2 16.0

' See note Table I. 1 See note o11able'I.

TABLE VI Yield of Butadiene, Mol Percent Composition, Weight Percent 1,130 F. 1,150 F. 1,170 F.

Hours after steaming K 00 MgO CuO FegO; 4 48 4 48 4 48 Catalyst III 20.0 57.4 4.2 18.4 15.1 12.3 18.6 17.8 18.8 17.8 Catalyst II 35.2 42.2 4.2 18.4 15.4 14.6 18.1 17.0 21.9 21.5

1 See note 01 Table I.

It is to be noted that during the series of cycles of approximately 42 hours average duration, the average conversion and average yield decreased less than 8 percent and the selectivity increased about 0.9 percent.

In Table III are presented a series of consecutive cycles with Catalyst IV:

TABLE 111 Hours M 01 Percent Average Since Age, Days 'Iempera- Steamture ing 1 Conver- Yield Selecsion tivity I See note of Table I.

It is to be noted that this catalyst quickly loses its activity under ordinary dehydrogenating conditions. For example, in the conversion column, starting at catalyst age 11.67 days, the percent conversion drops 011 from 28.1 at 4 hours after steaming to 10.6 at 44 hours after steaming. Again, at 16.54 days, the percent conversion drops from 24.2 at 4 hours after steaming to 13.4 at 23 hours after steaming. It is obvious that this catalyst must be steamed at substantially less than 24 hour intervals if the conversion is to be maintained at a reasonable level.

The results of additional runs and representative data from Tables I and II are presented in Tables IV, V and VI:

Referring to Table V, it is noted that Catalysts I, II and III retain their activity through extended periods of operation, whereas Catalyst IV is reduced to less than 40 percent of its original activity. This indicates the superiority of the high potassium catalyst. This table also shows the superiority of the chromium sesquioxide Catalyst I over the cupric oxide Catalyst 11 with the other components including potassium carbonate present in the same amounts in both catalysts.

Having thus described the invention by providing specific examples thereof, it is to be understood that no und-ue limitations or restrictions are to be implied by reason thereof and that many variations and modifications are clearly within the scope of the invention.

We claim:

1. A process for the dehydrogenation of a compound selected from the group consisting of mono-olefins, alkylpyridines and alkyl aromatics whichcomprises contacting said compound under dehydrogenating conditions with a catalyst comprising between about 30 percent and about 45 percent magnesium oxide, between about 10 percent and about 35 percent ferric oxide, between about 3 percent and about 6 percent, of a component selected from the group consisting of cupric oxide and chromium sesquioxide and at least about 30 percent potassium carbonate.

2. A process for the dehydrogenation of a compound selected from the group consisting of monoolefins, alkylpyridines and alkyl aromatics which comprises contacting said compound under dehydrogenating conditions with a catalyst comprising between about 30 percent and about 45 percent magnesium oxide, between about 10 percent and about 35 percent ferric oxide, between about 3 per cent and about 6 percent chromium sesquioxide and at least about 30 percent potassium carbonate.

3. A process for the dehydrogenation of a compound selected from the group consisting of monoelefins, alkylpyridines and alkyl aromatics which comprises contacting said compound at a temperature between about 1050 F. and about 1300" F., and a steam to olefin ratio of between about 5 to 1 and about'30 to 1 with a catalyst comprising between about 30 percent and about 45 percent magnesium oxide, between about 10 percent and about 35 percent ferric oxide, between about 3 percent and about 6 percent chromium sesquioxide and at least about 30 percent potassium carbonate.

4. A process for the dehydrogenation for monoolefins having 4 to 10 carbon atoms which comprises contacting said monoolefins at a temperature between about 1050 F. and about 1300' F. and a steam to olefin ratio of i? between about 5 to 1 andabout 30 to 1 with a catalyst comprising between about'30 percent and about 45 percent magnesium' oxide, between about 10 percent and about 35 percent ferric oxide, between about 3 percent and about 6 percent chromium sequioxide and at least about 30 percent potassium carbonate.

5. The processfor the dehydrogenation of butene to butadiene which comprises contacting normal butene at a temperature between about 1050 F. and about 1300 FQand a steam to olefin ratio of between about 5 to 1 and about 30 toy I with a catalyst comprising between about 30 percent and about 45 percent magnesium oxide, between about 10 percent and about .35 percent ferric oxide, between about 3 percent and about 6 percent chromium sesquionide and at least about 30' percent potassiurrr 2,541,671

carbonate. 4 I t References Cited in the file of this patent UNITED STATES PATENTS 2,393,537 Huffman 'J'an.' 22, 1946 2,395,876 Kearby Mar. 5, 1946 v Segura et a1. Feb. 13, 1951 2,567,296 Milligan et al. Sept. 11, 1951 i t l 

1. A PROCESS FOR THE DEHYDROGENATION OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF MONO-OLEFINS, ALKYLPYRIDINES AND ALKYL AROMATICS WHICH COMPRISES CONTACTING SAID COMPOUND UNDER DEHYDROGENATING CONDITIONS WITH A CATALYST COMPRISING BETWEEN ABOUT 30 PERCENT AND ABOUT 45 PERCENT MAGNESIUM OXIDE, BETWEEN ABOUT 10 PERCENT AND ABOUT 65 PERCENT FERRIC OXIDE, BETWEEN ABOUT 3 PERCENT AND ABOUT 6 PERCENT, OF A COMPONENT SELECTED FROM THE GROUP CONSISTING OF CUPRIC OXIDE AND CHROMIMUM SESQUIOXIDE AND AT LEAST ABOUT 30 PERCENT POTASSIUM CARBONATE. 